N-[(phosphinyl)amino]thio- and N-[(phosphinothioyl)amino]thiomethylcarbamates, a process for preparation and formulations of them suitable for pesticidal use are shown in U.S. Pat. No. 4,081,536, issued Mar. 28, 1978. Phosphoroaminosulfenyl derivatives of benzofuran carbamates and preparation thereof are disclosed in U.S. Pat. No. 4,024,277, issued Mar. 17, 1977. Additional N-[(phosphinyl or phosphinothioyl)amino]thiomethylcarbamates and pesticidal methods for use thereof are disclosed in U.S. application Ser. No. 962,266, filed Nov. 20, 1978. These phosphorus acid derivatives of aminothiomethylcarbamate pesticides are among the compounds prepared by the novel processes of the present invention and, therefore, the above patents and application can be referred to for relevant status of the art.
Other prior art includes a review of E. Kuhle, "One Hundred Years of Sulfenic Acid Chemistry I. Sulfenyl Halide Syntheses", Synthesis International Journal of Methods in Synthetic Organic Chemistry, No. 11, pp. 561-580 (November, 1970) and a disulfide preparation by M. V. Kalnins, "Reactions of Phthalimide and Potassium Phthalimide with Sulfur Monochloride", Can. J. Of Chem. Vol. 44, pp, 2111-2113 (1966). Although the review discloses numerous sulfenyl halides prepared by halogenation of organic disulfide, no compounds containing the phosphorus nitrogen sulfur linkage of the present invention are shown. Likewise, although Kalnins' discloses disulfides, the P--N--S linkage is not shown. The references P. I. Alimov, et al., "Derivatives of Diethoxyphosphorylamido-N-Sulfenic Acid", Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science, English Edition, pp. 1220-1221 (1964), translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya No. 7, pp. 1316-1317 (July, 1964) and P. I. Alimov, et al., "Synthesis of Some N-Sulfene Derivatives of the Amide of Diethylphosphoric Acid", Bulletin of the Academy of Science of the USSR, Division of Chemical Science, English Edition, pp. 1034-1036 (1964), translated from Izvestiya Akedemii Nauk, Otdelenie Khimicheskikh Nauk, No. 6, pp. 1132-1134 (June 1963) are also relevant. These references show the preparation of N-(sulfenechloro)ethylamide of diethylphosphoric acid and its reaction with simple amines and alcohols. However, contrary to the present invention the preparation is accomplished by the action of sulfuryl chloride on a disulfide precursor. A similar preparation using sulfuryl chloride is shown in U.S. Pat. No. 4,024,277 cited above.
The Alimov, et al, references disclose a limited number of disulfide species. Further, U.S. Pat. No. 4,024,277 shows a process which appears to prepare additional disulfides. However, selected disulfides of the present invention are novel compounds not taught by these references.
Further background teaching phosphoramide reactants denoted as Formula VI herein is found in Methoden der Organischen Chemie (Houben-Weyl) Volume 12, part 2, pages 610, 760 (thiophosphoramides) and pages 276, 413 (phosphoramides) George Thieme Verlag (Pub.), Stutgart, Germany, 1963. In addition, L. Anschiitz, et al. Ber. 61, 1264 (1928) teaches a benzothiophosphol chloride from which the corresponding amides of this invention can be made.